Method and device for growing large-volume oriented monocrystals

ABSTRACT

The invention relates to a method for growing large-volume monocrystals with a uniform orientation and consisting of a melt of crystal raw material, in a device comprising a sealable housing ( 10 ) in which a melting vessel ( 20 ) with side walls ( 22 ), a bottom ( 24 ), a top opening ( 26 ) facing said bottom ( 24 ) and optionally a lid ( 28 ) are located; and at least one heating element ( 50, 50 ′). According to said method, a crystal raw material in the melting vessel ( 20 ) is heated with heating elements ( 50, 50 ′) to a temperature above the melting point until a melt with a surface is formed. A monocrystal is then formed on the bottom of the melting vessel by lowering the temperature to at least the crystallisation point. Said monocrystal forms a solid/liquid interphase with the melt and grows towards the melt surface on said interphase, in a direction that is perpendicular to the interphase. An even interphase with a radius of curvature of at least one metre is produced during the crystal growing process by applying a vertical, axial temperature gradient between the bottom ( 24 ) of the melt vessel ( 20 ) and its top opening ( 26 ) and preventing heat from entering and/or leaving through the side walls ( 22 ).

[0001] The invention relates to a method for growing large-volume monocrystals of uniform orientation from a melt, to a device for carrying out this method and to the use of crystals prepared in this manner.

[0002] Monocrystals are characterized by the fact that they have a uniform orientation throughout their entire volume which is a prerequisite for high optical homogeneity within the entire crystal volume. For this reason, they are eminently suited for use in the optical industry or as starting material for optical components in deep-ultraviolet [DUV] photolithography, for example for steppers or excimer lasers.

[0003] The growing of monocrystals from a melt is in itself known. Text books about crystal growing, for example “Kristallzüjchtung” [The Growing of Crystals] by K. Th. Wilke and J. Bohm, which has 1088 pages, describe a wide variety of different methods for crystal growing of which the most common techniques will be mentioned briefly in the following. In principle, crystals can be grown from the gas phase, from the melt, from solutions or even from a solid phase by recrystallization or diffusion through a solid body. Such methods, however, are meant primarily for laboratory-scale work and not for large-scale industrial production. The most important large-scale melt growing processes for making crystals will be explained briefly in the following.

[0004] The Czochralski method involves dipping, with the aid of a finger-type tool, a slightly cooled seed crystal into a crucible containing molten crystal raw material and then pulling this seed crystal out slowly, preferably with rotation. In this manner, during the pulling, the seed crystal grows into a larger crystal.

[0005] The drawback of this method is that cooling produces relatively large temperature changes in the crystal resulting in stress-induced anisotropy.

[0006] By the vertical Bridgeman method, a crystal raw material is melted in a mobile melting crucible by means of a heating jacket. The crucible is then slowly lowered from the heating jacket through an axial temperature gradient produced by heaters. Or, alternatively, the crucible is stationary, and a mobile heating system is moved upward. The melt is thus cooled allowing the slow growth of an added seed crystal. In a variant of this method known as the Bridgeman-Stockbager method, a crystal is formed by slowly lowering the mobile crucible in an axial gradient between two heating jackets disposed above each other and between which exists a major temperature difference.

[0007] In the vertical gradient freeze method (VGF method), several concentric heating coils are disposed over each other around the stationary melting crucible so as to form a jacket. Each of these coils can be controlled separately. By slowly decreasing the heat output of each individual heating coil disposed around the crucible wall, the temperature is slowly reduced to below the crystallization point thus generating a radial temperature gradient along which crystal growth takes place.

[0008] In the gradient solidification method (GSM), a ring-shaped heating coil surrounding a stationary melting crucible is slowly moved downward and then upward.

[0009] Nevertheless, oriented monocrystals usually do not exhibit homogeneous optical and mechanical properties. It is desirable that such crystals be produced with a crystal orientation appropriate for a particular application. This, however, creates major problems in the production of large monocrystals, because during their growth such crystals spontaneously change their orientation, namely the position of their crystal axis. This leads to optically nonuniform crystals which do not exhibit the same light refraction in all regions.

[0010] Until now, while it was possible to produce crystals exhibiting some of these properties, it was not possible to grow large-volume uniformly oriented crystals that are free of convergences, are optically highly homogenous, exhibit high transmission and, in addition, do not discolor when exposed to a strong radiation source.

[0011] Attempts have been made by hitherto known methods, for example in the production of large calcium fluoride monocrystals, to grow the crystal in the direction of the {111} axis. This gave very low yields, however, namely only about 6-8% of the growing attempts gave a satisfactory crystal size. Because such crystal growing methods involve a process with a running time of approximately 6 weeks, and the number of such growing units is limited because of cost reasons, only low yields were achieved. Moreover, it was not possible by use of previously employed methods to produce large-volume monocrystals, particularly monocrystals extending far in all three directions in space, namely preferably round crystals with a diameter of >200 mm and a height of >100 mm, because such dimensions regularly lead to block formation within the crystal volume, namely a reorientation of the crystal axes takes place. Moreover, it has thus far not been possible to obtain satisfactorily such large crystals also in optically highly homogeneous form, namely so that their light refraction is the same in all regions. Another problem with such crystals is their radiation resistance, namely their ability not to undergo discoloration when exposed to a strong radiation source, for example a laser. This problem causes a decrease in yield, for example in the large-scale production of wafers.

[0012] It has already been attempted to produce large monocrystals by growing them in the shape of plates. EP-A-0 338 411, for example, describes an apparatus and a method for the controlled growing of large monocrystals in plate shape from a melt and by use of a melting crucible which has a rectangular cross-section and is configured so as to present two relatively wide and two relatively narrow side walls with heating devices disposed immediately adjacent to the wide sides. In this case, after the melting, the crucible is slowly lowered from the heating jacket by means of a lifting device as a result of which the crucible contents cool and crystallize. Although by this method it is possible to produce large oriented monocrystal plates, said plates do not adequately extend in all three directions in space.

[0013] Hence, the object of the invention is to produce large-volume crystals which are grown in any selected orientation along their {h,k,l} axes, preferably in the {111} or {112} orientation.

[0014] Another object of the invention is to produce large-volume crystals which extend far in all three directions in space.

[0015] According to the invention, this objective is reached by means of the method and device defined in the claims.

[0016] Surprisingly, we have now found that large-volume crystals can be produced by allowing them to cool with the aid of an axially disposed temperature gradient, namely a temperature gradient that is parallel to the growing direction, or with the aid of an axial heat flow while avoiding a radial, lateral heat flow perpendicular to it. In this manner, a nearly planar boundary is formed between the solid crystalline and the molten liquid phase. In contrast to this method, by the growing methods of the prior art, a lateral radial heat flow is predominantly formed, either as the only heat supply or heat removal or in combination with the heating elements disposed above and below a melting crucible.

[0017] The device according to the invention for growing large-volume monocrystals comprises a closable housing, a melting vessel contained therein and at least one heating element with a heat output sufficient to melt the crystal raw material present in the melting vessel and/or to keep the already molten crystal raw material in the molten state.

[0018] The melting vessel is preferably round. In special cases, however, a melting vessel with an oval or quadrangular cross-section may also be advantageous. The melting vessel comprises an internal receiving space or melting space formed by the bottom of the melting vessel, the side walls and an upper opening opposite the bottom.

[0019] In a particular embodiment of the invention, the upper opening opposite the bottom is closed by means of a cover. Said cover is preferably configured so that it does not rest on the side walls in gas-tight fashion, but so that the volatile impurities formed upon melting can leave the melting or crystal space. Laterally, around the melting crucible, there is disposed at least one element and preferably several elements which prevent a radial lateral heat flow. Preferably, the lateral elements are heat insulators, particularly those made of heat-insulating material. In a particular embodiment, the device according to the invention has a supporting heating system disposed laterally at a distance from the melting crucible, which is intended to prevent lateral heat flow. Advantageously, this supporting heating system is disposed at a distance from the melting vessel that is sufficient to prevent the generated heat from exerting any direct influence on the processes taking place in the melt. The supporting heating system only serves to equalize any temperature gradients arising between the melting crucible and the heat flow-preventing elements that surround said crucible, and the surroundings. Said supporting heating system is therefore usually separated from the walls of the melting crucible by an interposed layer of heat-insulating elements. Preferably, the supporting heating system is configured as a heating jacket.

[0020] The bottom of the melting vessel can be configured as desired. Usually, however, it is sloped downward in conical fashion. It thus forms a pyramid or preferably a cone, a truncated pyramid or cone being particularly preferred.

[0021] The bottom of the crucible is preferably provided with a downward protruding well which serves to receive a seed crystal of-a desired orientation. The seed crystal well is preferably disposed in the middle of the bottom, namely at the tip of the cone or pyramid. In a preferred embodiment of the invention, the seed crystal well has, particularly at its lower end, a cooling element. This cooling element is preferably a water-filled cooling element which during the melting of the crystal raw material protects the seed crystal present in the well from premature incipient or complete melting. In a preferred embodiment of the invention, the cooling element is heatable.

[0022] In a preferred embodiment of the invention, the melting crucible is provided above the melting space with a widened buffer space which serves as a funnel for charging the crystal raw material. In particular, however, it serves to equilibrate the heat given off by a cover heater to ensure that the heat flow produced will act uniformly on the crystal mass and that any local temperature differences arising at the heater will be corrected. Preferably, the actual melting space is provided with a heat-conducting cover separating the insulation space from the actual melting space. Said cover also serves to equilibrate the temperature and consists of an only slightly heat-insulating material.

[0023] The device according to the invention is provided with at least one heating element disposed above the melting vessel. Thanks to the insulation element enveloping the melting vessel and preventing a lateral heat flow, the heating of this heating element that is disposed above the melting vessel produces a heat flow which in the melting vessel runs exclusively axially. A lateral heat flow is prevented by the insulation elements. Advantageously, this upper heating element is a cover heater.

[0024] It has been found advantageous to provide a bottom heater at the bottom of the melting vessel in addition to the cover heater. In this manner, an even better axial heat flow or temperature gradient can be obtained between the cover heater and the bottom heater, a heat flow that can be adjusted with unusual sensitivity.

[0025] Advantageously, the bottom heater is disposed below the bottom of the melting vessel in a manner such that said heater does not include the seed crystal well or is at least disposed at a distance opposite said well in insulating fashion to prevent undesirable premature melting of the seed crystal.

[0026] In a preferred embodiment of the invention, all heating elements are enclosed in a jacket of insulating material surrounding the melting vessel, thus preventing an undesirable or uncontrolled heat flow.

[0027] It was found advantageous to provide one or more temperature-measuring elements disposed, if possible, closely adjacent to the outer wall of the melting vessel. Preferably, the measuring element(s) is (are) in the form of a sliding element(s) which during the operation of the system is (are) slidably disposed along the side wall to ensure measurement of the temperature gradient extending axially from the bottom of the vessel to the vessel cover. Preferred measuring elements are thermocouples, thermistors and particularly pyrometers.

[0028] In a particularly preferred embodiment, the device of the invention is provided with an arrangement enabling the boundary between the solid crystalline phase and the melted liquid phase to be determined. A phase feeler has been found advantageous for this purpose, said feeler comprising a feeling rod contained in a hollow guide tube extending into the melting vessel. The rod in the guide tube can be slowly lowered to feel the solid phase. In another preferred embodiment, the phase feeler consists of an ultrasonic device which dips into the melt from above and measures the sound waves reflected from the phase boundary, indicating crystal growth in this manner.

[0029] In another embodiment of the invention, the device is provided with a condenser disposed above the opening of the melting crucible, said condenser eliminating material vapors that may be escaping. In another preferred embodiment, the housing of the device of the invention is provided with a cover that can be opened and closed thus allowing the crystal raw material to be charged to the melting vessel and the finished crystal to be removed therefrom. Preferably, the housing of the device has at least one opening for admitting air to and removing air from the entire inner space. Through this opening, the inside of the device can be placed under vacuum and/or optionally filled with a protective gas.

[0030] The elements of the device of the invention disposed inside the housing preferably consist of graphite, the melting vessel being made of highly heat-conducting, pressed graphite. The insulating material preferably consists of loosely packed graphite, particularly fibrous material made of graphite wool or graphite mats. The heating elements are also advantageously made of graphite. The heat-producing, electrically conductive graphite strips wind in meander-like fashion around the surface to be heated and generate heat as electric resistance heaters. To prevent short circuits, the current-conducting elements are kept at a distance from the neighboring graphite parts by means of insulators. Boron nitride insulators are preferred for this purpose.

[0031] The housing of the apparatus of the invention usually consists of a chemically and heat-resistant material, preferably an alloy steel, high-quality alloy steel being particularly preferred. In many cases, however, structural steel was found to be adequate.

[0032] The invention also relates to a method -for producing large-volume monocrystals. According to the invention, said method comprises melting a crystal raw material mass in a vessel provided with a bottom, side walls, an upper opening and optionally a cover which at least partly closes the upper opening. In principle, it is also possible to introduce the already molten crystal raw material mass into the melting vessel.

[0033] According to the invention, to produce large-volume monocrystals, the melt is slowly cooled starting from the crucible bottom and in the direction of the melt surface or cover heater disposed above the melt surface. As a result, at the bottom of the vessel is formed a seed crystal which grows along the temperature gradient or along the heat flow axis. According to the invention, only a single heat flow or temperature gradient is formed between the bottom of the vessel and the melt surface. This means that, in the melting crucible, temperature surfaces facing each other are formed which are planar, the temperature increasing from the bottom of the crucible to the surface of the melt or cover heater, and the temperature being the same at all points within a temperature surface or temperature plane, namely not varying by more than 2° C. Preferably the increase in temperature between the bottom of the vessel and the surface of the melt is continuous. Should the surfaces wherein the temperature is constant exhibit a minimal curvature, the radius of this curvature is ≧1 m, radii of >2 m and particularly of >4 m being especially preferred.

[0034] In this manner, a phase boundary is formed between the solid, crystalline and the liquid, molten phase, said boundary forming along the temperature profile, namely parallel to the planes of equal temperature, and growing perpendicularly to said planes.

[0035] The phase boundary needed for the crystal growing according to the invention is obtained by preventing the formation of a lateral, namely radial heat flow. This is achieved with the aid of lateral elements, particularly elements disposed around the walls of the melting vessel. Such elements preferably consist of a supporting heater and/or an insulating material. It is particularly preferred to dispose along, and at a distance from, the side walls heating elements which serve exclusively to maintain the temperature. In this case, the interspace between the melting vessel and the heater disposed at a distance therefrom is filled with insulating material which on the one hand prevents lateral heat removal and thus the formation of a radial temperature gradient and, on the other, keeps the supporting heater from causing local overheating in the melting vessel. In essence, the supporting heater serves to counteract any heat loss through the insulating jacket thus supporting the maintenance of radial planarity of the temperature profile.

[0036] In principle, it is possible to form the axial heat flow formed by the method of the invention by means of a cover heater disposed above the crucible. It is preferable, however, also to heat the bottom of the crucible by means of a bottom heater so as to form a temperature gradient between the cover heater and the bottom heater.

[0037] According to the invention, it is preferred to promote crystal growth with the aid of a seed crystal placed at the bottom of the melting vessel. The seed crystal is preferably a monocrystal which is introduced into a seed crystal well connected to the bottom of the vessel and preferably so that the orientation of said seed crystal corresponds to the desired later orientation of the large-volume monocrystal. The melting is then carried out by turning on the cover heater and preferably the bottom heater so that the crystal raw material present in the vessel is melted. Optionally, the jacket heater is also turned on to provide support. The crucible is thus preferably heated to a temperature at which possibly present water of crystallization is released first. Thereafter, the temperature is raised further to remove any dissolved gases or gaseous constituents retained in the crystal raw material mass, as well as any gaseous decomposition products formed during the heat-up.

[0038] The melt is then homogenized over a prolonged period, preferably for at least one day. In particular, this is achieved by adjusting the heat output of the heating elements so that convection is generated in the melt which is thus continuously mixed. As a result, dissolved and undesirable impurities reach the melt surface wherefrom highly volatile substances, in particular, can vaporize off. Any crystal material that may be entrained is collected by means of a, preferably cooled, condenser. The homogenization of the melt is preferably carried out for at least two days and particularly for at least five days, at least one week being especially preferred.

[0039] During the melting and the homogenization, the seed crystal present in the seed crystal well is preferably cooled to prevent premature incipient or complete melting. This is usually accomplished by means of water cooling. Advantageously, the cooling is accomplished by means of a water-cooled graphite rod.

[0040] At the end of the melting and homogenization of the melt, the seed crystal is carefully melted. This is normally done in that the cooling is reduced and/or a seed crystal well heater is inserted. The seed crystal is carefully melted from the top downward so that a uniform transition arises between the seed crystal and the melt. The axial temperature gradient is then formed either by slowly lowering the heat output of the cover heater and/or of the bottom heater. Preferably, however, the cover heater is set at a temperature which is the same as, or is above or preferably slightly above, the crystallization temperature of the crystal to be produced. Advantageous cover heater temperatures are 200-300° C. above the crystallization temperature. The temperature of the bottom heater is advantageously at least 650° C. and preferably at least 900° C., but during the growing of the crystal is lower than the melt temperature. The heat output of the bottom heater is then slowly reduced. By reducing the bottom heater to a temperature below the crystallization temperature, the melt slowly cools along the axial temperature gradient, and the phase boundary formed at the plane of the crystallization temperature is slowly displaced in the melting vessel from the top downward causing the crystal to grow. In principle, it is also possible to reduce the temperature of the cover heater. In this case, the temperature is reduced at a rate for which the crystal growth occurs at 0.01 to 5 mm/hour, preferably 0.1 to 1 mm/hour and particularly 0.2 to 0.5 mm/hour. These values are usually achieved using a cooling rate of 0.001 to 5° C. per hour.

[0041] It has been found advantageous if during the growing process the temperature in the crystallized phase, namely in the grown crystal, does not exceed the temperature threshold at which a plastic form is produced. For this reason, the axial temperature gradient behind the phase boundary should be as flat as possible.

[0042] According to the invention, it has been found advantageous to form in the lower, conical part of the bottom of the melting crucible, namely in the part forming the bottom between the seed crystal well and the wall of the crucible, a nonplanar phase boundary curved upward toward the cover and having a curvature radius of <1 m, preferably <0.8 m and particularly <0.5 m.

[0043] After the monocrystal has been produced in this manner, it is annealed. As a result, any crystal nonhomogeneities are removed at an elevated temperature, namely the crystal defects are repaired at this temperature. After the growing and annealing of the crystal, the entire large-volume monocrystal is slowly cooled to room temperature. Such cooling is usually carried out over several days to several weeks and, depending on the phase and stage, preferably at a cooling rate from about 0.001° C./hour to 15° C./hour, particularly to 10° C./hour and advantageously to 1° C./hour, with 0.01° C./hour to 8° C./hour and particularly 3° C./hour being preferred. For the cooling, too, an essentially axial temperature gradient is preferably retained. In this case, however, the lateral support heating may optionally be omitted. Such slow cooling affords large-volume crystals which are unusually free of stress. The cooling rate is preferably controlled by means of several temperature sensors disposed in the device of the invention. In this manner, the temperature course during cooling can also be controlled. As for crystal growing, this is advantageously done with the aid of a computer.

[0044] The crystal raw material used for the method of the invention comprises, in particular, raw materials containing in addition to the crystal material also scavengers which during a homogenization phase react with possibly present impurities to form readily volatile substances. Preferred crystal materials are MgF₂, BaF₂, SrF₂, LiF and NaF, with CaF₂ being particularly preferred. The method of the invention affords large-volume monocrystals with a diameter of at least 200 mm, preferably at least 250 mm and particularly at least 300 mm and with a height of at least 100 mm, preferably 130 mm and particularly at least 140 mm. The optical homogeneity attained throughout the entire crystal volume is unusually, high, meaning that the maximum refractive index variation throughout the crystal volume corresponds to a maximum difference Δn of ≦3×10⁻⁶, preferably >2×10⁻⁶ and particularly >1×10⁻⁶, the stress birefringence SBR being <3 nm/cm and particularly <2 nm/cm and especially <1 nm/cm.

[0045] The method of the invention is preferably carried out in a vacuum between 10⁻³ and 10⁻⁶ mbar (corresponding to 10⁻¹ to 10⁻⁴ Pa) and preferably between 10⁻⁴ and 10⁻⁵ mbar (10⁻² to 10⁻³ Pa). It is particularly preferred to carry out the method of the invention in an atmosphere of protective gas, particularly in a nonoxidizing atmosphere. To this end, the entire apparatus of the invention is flushed before or also during the heating with inert gas or an inert gas mixture.

[0046] In carrying out the method of the invention, the device of the invention is preferably mounted in shock-free fashion. During operation, the melting vessel and the heating elements are firmly mounted in an unchangeable, relationship to each other.

[0047] The large-volume crystals obtained by the method of the invention are particularly well suited for the production of optical components for DUV lithography and for the production of wafers covered with photoresist and thus for the production of electronic devices. Hence, the invention also relates to the use of monocrystals made by the method of the invention and/or in the device of the invention for the production of lenses, prisms, light-conducting rods, optical windows and optical devices for DUV lithography and particularly for the production of steppers and excimer lasers and thus also for the production of integrated circuits and electronic devices such as computers containing computer chips as well as for other electronic devices containing chip-like integrated circuits.

[0048] The invention will now be explained in greater detail by way of the following figures and example.

[0049]FIG. 1 shows a device of the invention for growing large-volume crystals,

[0050]FIG. 2 shows a monocrystal produced with this device and having a diameter of 385 mm and a height of about 160 mm,

[0051]FIG. 3 shows monocrystal slices obtained from the monocrystal of FIG. 2.

[0052] As shown in FIG. 1, the device of the invention comprises a special double-wall housing 10 wherein is disposed melting crucible 20 made of pressed graphite. Melting crucible 20 has an inner space 30 (melting and crystallization space) defined by walls 22 which form a conical bottom 24 shaped as a truncated cone and by an upper crucible opening 26 which is partly closed by a cover 28. In the upper part of the melting crucible is disposed a funnel-shaped buffer space 40 made of the same material as melting crucible 20 and connected to it, preferably so as to form a single piece. Buffer space 40 itself also has side walls 42, a cover 48 and a bottom 44 which is connected with side walls 22 of melting crucible 20. Above buffer space 40 is disposed a cover heater 50, 50′ located opposite bottom heater 52. Bottom heater 52 is disposed to the side of seed crystal well 32 and is kept at a distance therefrom to prevent the premature melting of the seed crystal contained therein. On the bottom, the seed crystal well contains a water-cooled graphite rod 70. Laterally to the seed crystal well and to water-cooled graphite rod 70 are disposed lateral heating elements 56 for the intentional melting of the seed crystal. Moreover, laterally to melting crucible 20 is disposed a temperature-measuring element 60 configured as a sliding element, whereby the axial temperature course can be accurately determined.

[0053] Side walls 22 of vessel 20 are completely surrounded by insulating jacket 82. Insulating jacket 82 is located at a distance from a lateral, jacket-like supporting heater 54. Heating elements 50, 50′, 52, 54 and 56 and melting crucible 20 with seed crystal well 32 and the buffer part 40 disposed above it are surrounded by an insulating material 80 consisting of graphite which prevents lateral heat flow and only permits the formation of an axial temperature gradient between the cover heater and melting crucible bottom 24 or bottom heater 52.

[0054] The device of the invention also has an opening, not shown, for flushing with an inert gas or for applying vacuum. To determine the size of the growing crystal or the position of the phase boundary, there is provided a phase feeler 90 which extends from the outside through the housing and contains rod 94 slidably disposed in outer tube 92, said rod being capable of being slowly moved downward and of feeling the solid phase boundary. In principle, tube 92 can also be connected with rod 94. To separate the impurities removed during homogenization, condenser 95 is disposed above the melting crucible.

EXAMPLE 1

[0055] To produce a calcium fluoride monocrystal, inner space 30 of melting vessel 20 was filled with a calcium fluoride mixture which in addition contained scavenger materials with high affinity for oxygen, such as PbF₂, SnF₂ or CdF₂. The device was then closed with a cover not shown in FIG. 1 and was flushed with nitrogen as inert gas to remove the undesirable atmospheric oxygen. A vacuum of 10⁻⁴ mbar (10⁻² Pa) was then applied and, while cooling the seed crystal well, cover heater 50, 50′, bottom heater 52 and optionally jacket heater 54 were put in place and slowly heated to 1450° C. over a period of several hours. The melt was then homogenized at this temperature for five days while maintaining convection in it. After the homogenization, the bottom heater was reduced to a temperature of 1200° C., and the seed crystal was carefully melted with the aid of seed crystal well heater 26. After turning off the seed crystal well heater, cover heater 50, 50′ was kept constant while the bottom heater was made to cool slowly, over a period of several days, to a temperature below the crystallization point, causing a monocrystal to grow from the seed crystal in the direction of the melt surface. The resulting monocrystal had the same orientation as the seed crystal. After the entire melt had solidified with formation of a monocrystal, the resulting monocrystal was annealed and cooled to room temperature over a period of three weeks. In this manner, a monocrystal was obtained which had a diameter of 385 cm [sic—“mm” seems to be meant—Translator] and a height of 161 mm (without seed crystal well). The monocrystal showed throughout the entire crystal volume a refractive index variation Δn <1×10⁻⁶. The stress birefringence SBR was <1 nm/cm. Moreover, the crystal thus obtained had an unusually high radiation resistance. 

1. Device for growing large-volume monocrystals which comprises a housing (10) with a closable charging and discharging opening as well as a melting vessel (20) disposed therein and enclosing a melting space (30) formed by a bottom (24), side walls (22) and an upper opening (26) opposite the bottom, said melting space (30) optionally being provided with a cover (28), as well as at least one heating element (50, 50′) for melting the crystal raw material mass present in the melting space (30) and/or for maintaining the molten state of an already molten crystal raw material mass, the heating element (50, 50′) being disposed above the melting vessel (20) and generating a heatflow extending axially between the bottom (24) and the opening (26) of the melting vessel, characterized in that at least one element (82), (54) is disposed at the side walls (22) so as to prevent a lateral, radial heat flow.
 2. Device according to claim 1, characterized in that the elements disposed at the side walls (22) prevent the formation of a lateral heat flow to the extent that during crystal growth a planar solid/liquid phase boundary with a curvature radius of ≧1 m is formed.
 3. Device according to one of the preceding claims, characterized in that the bottom (24) of the melting vessel (20) has a conical shape.
 4. Device according to one of the preceding claims, characterized in that the bottom (24) of the melting crucible (20) is provided with a well for receiving a seed crystal.
 5. Device according to one of the preceding claims, characterized in that a cooling element is disposed at the seed crystal well.
 6. Device according to one of the preceding claims, characterized in that a temperature-measuring element (60) is provided at the side wall (22) of the melting vessel (20).
 7. Device according to one of the preceding claims, characterized in that it comprises an element (90) for feeling the solid/liquid phase boundary.
 8. Device according to one of the preceding claims, characterized in that the heating elements, insulation material or melting crucibles are made of graphite.
 9. Device according to one of the preceding claims, characterized in that it contains a supporting heater disposed at a distance from the side walls (22) of the melting vessel.
 10. Method for growing large-volume monocrystals with uniform orientation from a melt of crystal raw material in a device comprising a closable housing (10) with, disposed therein, side walls (22), a bottom (24), an upper opening (26) opposite the bottom (24) and a melting vessel (20) optionally-with a cover (28), as well as at least one heating element (50, 50′), whereby a crystal raw material present in the melting vessel (20) is heated by means of heating elements (50, 50′) at a temperature above the melting point until a melt with a surface is formed and/or whereby already molten crystal raw material is introduced into the melting vessel, and thereafter, by lowering the temperature to at least the crystallization point, a monocrystal is formed at the bottom of the melting vessel, said monocrystal forming a solid/liquid phase boundary at which the monocrystal grows toward the surface of the melt in the direction perpendicular to the phase boundary, characterized in that for the crystal growing a planar phase boundary with a curvature diameter of at least one meter is formed by providing a vertical axial temperature gradient between the bottom (24) of the melting vessel (20) and the upper opening (26) thereof and by preventing heat inflow and/or heat outflow through the side walls (22).
 11. Method according to claim 10, characterized: in that the direction of growth is set in advance by means of a seed crystal.
 12. Method according to one of the preceding claims, characterized in that the {111} or {112} crystal axis is used as the growth direction.
 13. Method according to one of the preceding claims, characterized in that the axial temperature gradient is formed between a bottom heater (52) and the cover heater (50, 50′).
 14. Method according to one of the preceding claims, characterized in that a crystal growth rate of 0.1 to 1 mm/hr is produced by slowly reducing the heat from the bottom heater (52).
 15. Method according to one of the preceding claims, characterized in that the temperature of the bottom heater (52) is kept at the most 10° C. below the melting temperature.
 16. Method according to one of the preceding claims, characterized in that the melt and/or the finished crystal is cooled at a rate of 0.1 to 5° C. per day.
 17. Method according to one of the preceding claims, characterized in that after the charging of the crystal raw material the system is flushed with an inert gas and/or the crystal growing is carried out under vacuum.
 18. Method according to one of the preceding claims, characterized in that calcium fluoride is used as the crystal raw material.
 19. Method according to one of the preceding claims, characterized in that one or more scavengers are added to the crystal raw material.
 20. Method according to one of the preceding claims, characterized in that lateral heat flow is prevented by means of a supporting heater (54) kept at a distance from the crucible walls by means of a heat insulator (82).
 21. Method according to one of the preceding claims, characterized in that at the beginning of crystal growing the bottom heater is heated to a temperature of at least 650° C. and the cover heater to a temperature of at least 1590° C.
 22. Method according to one of the preceding claims, characterized in that before the beginning the crystallization the melt is homogenized over a period of 1 to 20 days.
 23. Method according to one of -the preceding claims, characterized in that the upper heater is kept at a constant temperature while the lower heater is slowly cooled.
 24. Use of monocrystals obtained by the method according to claims 1-23 for producing lenses, prisms, light-conducting rods, optical windows as well as optical components for DUV photolithography, steppers, excimer lasers, wafers, computer chips, as well as integrated circuits and electronic devices containing such circuits and chips. 